U.S. patent application number 10/044255 was filed with the patent office on 2003-02-20 for fungicidal mixtures based on amide compounds and pyridine derivatives.
Invention is credited to Ammermann, Eberhard, Eicken, Karl, Hampel, Manfred, Lorenz, Gisela, Schelberger, Klaus, Scherer, Maria, Strathmann, Siegfried.
Application Number | 20030036480 10/044255 |
Document ID | / |
Family ID | 7852427 |
Filed Date | 2003-02-20 |
United States Patent
Application |
20030036480 |
Kind Code |
A1 |
Schelberger, Klaus ; et
al. |
February 20, 2003 |
Fungicidal mixtures based on amide compounds and pyridine
derivatives
Abstract
Fungicidal mixtures comprise as active components a) an amide
compound of the formula I A--CO--NR.sup.1R.sup.2 I in which A is an
aryl group or an aromatic or non-aromatic, 5- or 6-membered
heterocycle which has from 1 to 3 hetero atoms selected from O, N
and S; where the aryl group or the heterocycle may or may not have
1, 2 or 3 substituents which are selected, independently of one
another, from alkyl, halogen, CHF.sub.2, CF.sub.3, alkoxy,
haloalkoxy, alkylthio, alkylsulfynyl and alkylsulfonyl; R.sup.1 is
a hydrogen atom; R.sup.2 is a phenyl or cycloalkyl group which may
or may not have 1, 2 or 3 substituents which are selected,
independently of one another, from alkyl, alkenyl, alkynyl, alkoxy,
alkenyloxy, alkynyloxy, cycloalkyl, cycloalkenyl, cycloalkyloxy,
cycloalkenyloxy, phenyl and halogen, where the aliphatic and
cycloaliphatic radicals may be partially or fully halogenated
and/or the cycloaliphatic radicals may be substituted by from 1 to
3 alkyl groups and where the phenyl group may have from 1 to 5
halogen atoms and/or from 1 to 3 substituents which are selected,
independently of one another, from alkyl, haloalkyl, alkoxy,
haloalkoxy, alkylthio and haloalkylthio, and where the amidic
phenyl group may or may not be condensed with a saturated
5-membered ring which may or may not be substituted by one or more
alkyl groups and/or may have a hetero atom selected from O and S,
and and [sic] b) fungicides from the group of the dicarboximides
and/or c) pyrimidine derivatives of the formula III 1 in which R is
methyl, propyn-1-yl or cyclopropyl, and/or d) fludioxinil or
fenpiclonil and/or e) captan, captafol or folpet and/or f)
fluazinam and/or g) dichlofluanid or tolylfluanid in a
synergistically effective amount.
Inventors: |
Schelberger, Klaus;
(Gonnheim, DE) ; Scherer, Maria; (Landau, DE)
; Eicken, Karl; (Wachenheim, DE) ; Hampel,
Manfred; (Neustadt, DE) ; Ammermann, Eberhard;
(Heppenheim, DE) ; Lorenz, Gisela; (Neustadt,
DE) ; Strathmann, Siegfried; (Limburgerhof,
DE) |
Correspondence
Address: |
Herbert B. Keil
KEIL & WEINKAUF
1101 Connecticut Avenue, N.W.
Washington
DC
20036
US
|
Family ID: |
7852427 |
Appl. No.: |
10/044255 |
Filed: |
January 14, 2002 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
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10044255 |
Jan 14, 2002 |
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09581833 |
Jun 19, 2000 |
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6365608 |
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09581833 |
Jun 19, 2000 |
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PCT/EP98/08231 |
Dec 15, 1998 |
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Current U.S.
Class: |
504/130 |
Current CPC
Class: |
A01N 43/40 20130101;
A01N 43/40 20130101; A01N 43/40 20130101; A01N 43/40 20130101; A01N
43/40 20130101; A01N 43/54 20130101; A01N 43/40 20130101; A01N
2300/00 20130101; A01N 37/32 20130101; A01N 47/04 20130101; A01N
43/36 20130101; A01N 43/40 20130101; A01N 43/36 20130101; A01N
43/76 20130101; A01N 37/32 20130101; A01N 43/40 20130101; A01N
43/54 20130101; A01N 47/04 20130101; A01N 47/04 20130101; A01N
43/54 20130101; A01N 37/32 20130101; A01N 43/54 20130101; A01N
47/38 20130101; A01N 43/36 20130101; A01N 37/32 20130101; A01N
43/40 20130101; A01N 43/36 20130101; A01N 47/04 20130101; A01N
53/00 20130101; A01N 43/40 20130101 |
Class at
Publication: |
504/130 |
International
Class: |
A01N 043/40 |
Foreign Application Data
Date |
Code |
Application Number |
Dec 18, 1997 |
DE |
19756379.1 |
Claims
We claim:
1. A fungicidal mixture, comprising as active components a) an
amide compound of the formula I A--CO--NR.sup.1R.sup.2 I in which A
is an aryl group or an aromatic or non-aromatic, 5- or 6-membered
heterocycle which has from 1 to 3 hetero atoms selected from O, N
and S; where the aryl group or the heterocycle may or may not have
1, 2 or 3 substituents which are selected, independently of one
another, from alkyl, halogen, CHF.sub.2, CF.sub.3, alkoxy,
haloalkoxy, alkylthio, alkylsulfynyl and alkylsulfonyl; R.sup.1 is
a hydrogen atom; R.sup.2 is a phenyl or cycloalkyl group which may
or may not have 1, 2 or 3 substituents which are selected,
independently of one another, from alkyl, alkenyl, alkynyl, alkoxy,
alkenyloxy, alkynyloxy, cycloalkyl, cycloalkenyl, cycloalkyloxy,
cycloalkenyloxy, phenyl and halogen, where the aliphatic and
cycloaliphatic radicals may be partially or fully halogenated
and/or the cycloaliphatic radicals may be substituted by from 1 to
3 alkyl groups and where the phenyl group may have from 1 to 5
halogen atoms and/or from 1 to 3 substituents which are selected,
independently of one another, from alkyl, haloalkyl, alkoxy,
haloalkoxy, alkylthio and haloalkylthio, and where the amidic
phenyl group may or may not be condensed with a saturated
5-membered ring which may or may not be substituted by one or more
alkyl groups and/or may have a hetero atom selected from O and S,
and and [sic]b) fungicides from the group of the dicarboximides
and/or c) a pyrimidine derivative of the formula III, 18in which R
is methyl, propyn-1-yl or cyclopropyl, and/or d) at least one
active ingredient of the formula IV or V, 19and/or e) a phthalimide
derivative selected from the group consisting of the compounds VIa,
VIb and VII 20and/or f) a dinitroaniline of the formula VIII
21and/or g) an arylsulfamide of the formula IX a or IXb 22 in a
synergistically effective amount.
2. A fungicidal mixture as claimed in claim 1, wherein in the
formula I the radical A is one of the following groups: phenyl,
pyridyl, dihydropyranyl, dihydrooxathiynyl, dihydrooxathiynyloxide,
dihydrooxathiynyldioxide, furyl, thiazolyl, pyrazolyl or oxazolyl,
where these groups may have 1, 2 or 3 substituents which are
selected, independently of one another, from alkyl, halogen,
difluoromethyl and trifluoromethyl.
3. A fungicidal mixture as claimed in claim 1, wherein in the
formula I the radical A is one of the following groups:
pyridin-3-yl, which may or may not be substituted in the 2-position
by halogen, methyl, difluoromethyl, trifluoromethyl, methoxy,
methylthio, methylsulfynyl or methylsulfonyl; phenyl, which may or
may not be substituted in the 2-position by methyl,
trifluoromethyl, chlorine, bromine or iodine;
2-methyl-5,6-dihydropyran-3-yl;
2-methyl-5,6-dihydro-1,4-oxathiyn-3-yl or the 4-oxide or
4,4-dioxide thereof; 2-methylfuran-3-yl, which may or may not be
substituted in the 4- and/or 5-position by methyl; thiazol-5-yl,
which may or may not be substituted in the 2- and/or 4-position by
methyl, chlorine, difluoromethyl or trifluoromethyl; thiazol-4-yl,
which may or may not be substituted in the 2- and/or 5-position by
methyl, chlorine, difluoromethyl or trifluoromethyl;
1-methylpyrazol-4-yl, which may or may not be substituted in the 3-
and/or 5-position by methyl, chlorine, difluoromethyl or
trifluoromethyl; or oxazol-5-yl, which may or may not be
substituted in the 2- and/or 4-position by methyl or chlorine.
4. A fungicidal mixture as claimed in one of the preceding claims,
which comprises a compound of the formula I in which R.sup.2 is a
phenyl group which may or may not be substituted by 1, 2 or 3 of
the substituents mentioned in claim 1.
5. A fungicidal mixture as claimed in claim 4, where R.sup.2 is a
phenyl group which has one of the following substituents in the
2-position: C.sub.3-C.sub.6-alkyl, C.sub.5-C.sub.6-cycloalkenyl,
C.sub.5-C.sub.6-cycloalkyloxy, cycloalkenyloxy, where these groups
may be substituted by 1, 2 or 3 C.sub.1-C.sub.4-alkyl groups,
phenyl which is substituted by from 1 to 5 halogen atoms and/or
from 1 to 3 groups which are selected, independently of one
another, from C.sub.1-C.sub.4-alkyl, C.sub.1-C.sub.4-haloalkyl,
C.sub.1-C.sub.4-alkoxy, C.sub.1-C.sub.4-haloalkoxy,
C.sub.1-C.sub.4-alkylthio and C.sub.1-C.sub.4-haloalkylthio, or
where R.sup.2 is indanyl or oxaindanyl which may or may not be
substituted by 1, 2 or 3 C.sub.1-C.sub.4-alkyl groups.
6. A fungicidal mixture as claimed in any of claims 1 to 5, which
comprises an amide compound of the formula Ia below: 23in which A
is 24X is methylene, sulfur, sulfynyl or sulfonyl (SO.sub.2),
R.sup.3 is methyl, difluoromethyl, trifluoromethyl, chlorine,
bromine or iodine, R.sup.4 is trifluoromethyl or chlorine, R.sup.5
is hydrogen or methyl, R.sup.6 is methyl, difluoromethyl,
trifluoromethyl or chlorine, R.sup.7 is hydrogen, methyl or
chlorine, R.sup.8 is methyl, difluoromethyl or trifluoromethyl,
R.sup.9 is hydrogen, methyl, difluoromethyl, trifluoromethyl or
chlorine, R.sup.10 is C.sub.1-C.sub.4-alkyl,
C.sub.1-C.sub.4-alkoxy, C.sub.1-C.sub.4-alkylthio or halogen.
7. A fungicidal mixture as claimed in any of claims 1 to 5, which
comprises as amide compound a compound of the formula Ib below:
25in which R.sup.4 is halogen and R.sup.11 is phenyl which is
substituted by halogen.
8. A fungicidal mixture as claimed in claim 1, which comprises as
amide compound a compound of the formulae below: 26
9. A fungicidal mixture as claimed in any of the preceding claims,
comprising as fungicide from the group of the dicarboximides one or
more of the compounds IIa to IId II.a: ethyl
(")-3-(3,5-dichlorophenyl)-5-meth-
yl-2,4-dioxooxazolidine-5-carboxylate [sic] 27 or II.b:
3-(3,5-dichlorophenyl)-N-isopropyl-2,4-dioxoimidazolidine-1-carboxamide
28 or II.c:
N-(3,5-dichlorophenyl)-1,2-dimethylcyclopropane-1,2-dicarboxi- mide
29 or II.d:
(RS)-3-(3,5-dichlorophenyl)-5-ethenyl-5-methyl-1,3-oxazo-
lidine-2,4-dione 30
10. A fungicidal mixture as claimed in any of the preceding claims,
which is conditioned in two parts, one part comprising the amide
compound I in a solid or liquid carrier and the other part
comprising one or more compounds of the formulae IIa to IXb in a
solid or liquid carrier.
11. A method for controlling harmful fungi, which comprises
treating the fungi, their habitat, or the materials, plants, seeds,
soils, areas or spaces to be protected against fungal attack with a
fungicidal mixture as claimed in any of claims 1 to 9, where the
application of the active ingredients amide compound I and one or
more compounds of the formulae IIa to IXb may be carried out
simultaneously, that is either together or separately, or in
succession.
Description
[0001] The present invention relates to fungicidal mixtures for
controlling harmful fungi, which mixtures comprise amide compounds
of the formula I
[0002] A--CO--NR.sup.1R.sup.2 (I)
[0003] in which
[0004] A is an aryl group or an aromatic or non-aromatic, 5- or
6-membered heterocycle which has from 1 to 3 hetero atoms selected
from O, N and S;
[0005] where the aryl group or the heterocycle may or may not have
1, 2 or 3 substituents which are selected, independently of one
another, from alkyl, halogen, CHF.sub.2, CF.sub.3, alkoxy,
haloalkoxy, alkylthio, alkylsulfynyl and alkylsulfonyl;
[0006] R.sup.1 is a hydrogen atom;
[0007] R.sup.2 is a phenyl or cycloalkyl group which may or may not
have 1, 2 or 3 substituents which are selected from alkyl, alkenyl,
alkynyl, alkoxy, alkenyloxy, alkynyloxy, cycloalkyl, cycloalkenyl,
cycloalkyloxy, cycloalkenyloxy, phenyl and halogen, where the
aliphatic and cycloaliphatic radicals may be partially or fully
halogenated and/or the cycloaliphatic radicals may be substituted
by from 1 to 3 alkyl groups and where the phenyl group may have
from 1 to 5 halogen atoms and/or from 1 to 3 substituents which are
selected, independently of one another, from alkyl, haloalkyl,
alkoxy, haloalkoxy, alkylthio and haloalkylthio, and where the
amidic phenyl group may or may not be condensed with a saturated
5-membered ring which may or may not be substituted by one or more
alkyl groups and/or may have a hetero atom selected from O and
S,
[0008] and
[0009] b) fungicides of the group of the dicarboximides
[0010] and/or
[0011] c) a pyrimidine derivative of the formula III, 2
[0012] in which R is methyl, propyn-1-yl or cyclopropyl,
[0013] and/or
[0014] d) at least one active ingredient of the formula IV or V,
3
[0015] and/or
[0016] e) a phthalimide derivative selected from the group
consisting of the compounds VIa, VIb and VII 4
[0017] and/or
[0018] f) a dinitroaniline of the formula VIII 5
[0019] and/or
[0020] g) an arylsulfamide of the formula IX a or IXb 6
[0021] in a synergistically effective amount.
[0022] WO 97/08952 describes fungicidal mixtures which, in addition
to compounds of the formula I, also comprise fenazaquin as further
components. These are described as being very effective against
Botrytis.
[0023] The amide compounds of the formula I are known per se and
are described in the literature (EP-A 545 099).
[0024] Fungicides from the group of the dicarboximides are known to
the person skilled in the art and are commercially available.
[0025] Also known are the pyrimidine derivatives III, their
preparation and their activity against harmful fungi [R=methyl:
DD-A 151 404 (common name: pyrimethanil); R=1-propynyl: EP-A 224
339 (common name: mepanipyrim); R=cyclopropyl: EP-A 310 550].
[0026] The compound IV is known from K. Gehmann, R. Nyfeler, A. J.
Leadbeater, D. Nevill and D. Sozzi, Proceedings of the Brighton
Crop Protection Conference, Pests and Diseases 1990, Vol. 2, p. 399
(common name: fludioxinil) and is commercially available from
Novartis.
[0027] The compound V is known from D. Nevill, R. Nyfeler, D.
Sozzi, Proceedings of the Brighton Crop Protection Conference,
Pests and Diseases 1988, Vol. 1, p. 65 (common name:
fenpiclonil).
[0028] U.S. Pat. Nos. 2,553,770; 2,553,771; 2,553,776 describe the
compounds VIa (common name: captan) and VII (common name: folpet),
their preparation and their activity against harmful fungi. The
compound VIb (common name: captafol) is described in Phytopathology
52(1962), 52, 754.
[0029] Likewise, the compound VIII, its preparation and its use
(CAS RN 79622-59-6, common name: fluazinam) are described in the
literature.
[0030] The compounds IXa and IXb are known under the common names
dichlofluanid and tolylfluanid, respectively, and are described in
the German patent 1193498.
[0031] It is an object of the present inventions [sic] to provide
mixtures which have an improved activity against harmful fungi
combined with a reduced total amount of active ingredients applied
(synergistic mixtures), with a view to reducing the application
rates and to improving the activity spectrum of the known
compounds.
[0032] We have found that this object is achieved by the mixtures
defined at the outset. Moreover, we have found that better control
of harmful fungi is possible by applying the compounds I and the
compounds II to VIII simultaneously, that is either together or
separately, or by applying the compounds I and the compounds II to
VIII in succession than when the compounds I or II to VIII are
applied on their own.
[0033] The mixtures according to the invention have synergistic
action and are therefore particularly suitable for controlling
harmful fungi, in particular of Botrytis species.
[0034] In the context of the present invention, halogen is
fluorine, chlorine, bromine and iodine and is in particular
fluorine, chlorine and bromine.
[0035] The term "alkyl" includes straight-chain and branched alkyl
groups. These are preferably straight-chain or branched
C.sub.1-C.sub.12-alkyl and in particular C.sub.1-C.sub.6-alkyl
groups. Examples of alkyl groups are alkyl such as, in particular,
methyl, ethyl, propyl, 1-methylethyl, butyl, 1-methylpropyl,
2-methylpropyl, 1,1-dimethylethyl, n-pentyl, 1-methylbutyl,
2-methylbutyl, 3-methylbutyl, 1,2-dimethylpropyl,
1,1-dimethylpropyl, 2,2-dimethylpropyl, 1-ethylpropyl, n-hexyl,
1-methylpentyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl,
1,2-dimethylbutyl, 1,3-dimethylbutyl, 2,3-dimethylbutyl,
1,1-dimethylbutyl, 2,2-dimethylbutyl, 3,3-dimethylbutyl,
1,1,2-trimethylpropyl, 1,2,2-trimethylpropyl, 1-ethylbutyl,
2-ethylbutyl, 1-ethyl-2-methylpropyl, n-heptyl, 1-methylhexyl,
1-ethylpentyl, 2-ethylpentyl, 1-propylbutyl, octyl, decyl,
dodecyl.
[0036] Haloalkyl is an alkyl group as defined above which is
partially or fully halogenated by one or more halogen atoms, in
particular by fluorine and chlorine. Preferably, there are from 1
to 3 halogen atoms present, and the difluoromethane [sic] or the
trifluoromethyl group is particularly preferred.
[0037] The above statements for the alkyl group and the haloalkyl
group apply in a corresponding manner to the alkyl and haloalkyl
groups in alkoxy, haloalkoxy, alkylthio, haloalkylthio,
alkylsulfynyl and alkylsulfonyl.
[0038] The alkenyl group includes straight-chain and branched
alkenyl groups. These are preferably straight-chain or branched
C.sub.3-C.sub.12-alkenyl groups and in particular
C.sub.3-C.sub.6-alkenyl groups. Examples of alkenyl groups are
2-propenyl, 2-butenyl, 3-butenyl, 1-methyl-2-propenyl,
2-methyl-2-propenyl, 2-pentenyl, 3-pentenyl, 4-pentenyl,
1-methyl-2-butenyl, 2-methyl-2-butenyl, 3-methyl-2-butenyl,
1-methyl-3-butenyl, 2-methyl-3-butenyl, 3-methyl-3-butenyl,
1,1-dimethyl-2-propenyl, 1,2-dimethyl-2-propenyl,
1-ethyl-2-propenyl, 2-hexenyl, 3-hexenyl, 4-hexenyl, 5-hexenyl,
1-methyl-2-pentenyl, 2-methyl-2-pentenyl, 3-methyl-2-pentenyl,
4-methyl-2-pentenyl, 1-methyl-3-pentenyl, 2-methyl-3-pentenyl,
3-methyl-3-pentenyl, 4-methyl-3-pentenyl, 1-methyl-4-pentenyl,
2-methyl-4-pentenyl, 3-methyl-4-pentenyl, 4-methyl-4-pentenyl,
1,1-dimethyl-2-butenyl, 1,1-dimethyl-3-butenyl,
1,1-dimethyl-3-butenyl [sic], 1,2-dimethyl-2-butenyl,
1,2-dimethyl-3-butenyl, 1,3-dimethyl-2-butenyl,
1,3-dimethyl-3-butenyl, 2,2-dimethyl-3-butenyl,
2,3-dimethyl-2-butenyl, 2,3-dimethyl-3-butenyl, 1-ethyl-2-butenyl,
1-ethyl-3-butenyl, 2-ethyl-2-butenyl, 2-ethyl-3-butenyl,
1,1,2-trimethyl-2-propenyl, 1-ethyl-1-methyl-2-propenyl and
1-ethyl-2-methyl-2-propenyl, in particular 2-propenyl, 2-butenyl,
3-methyl-2-butenyl and 3-methyl-2-pentenyl.
[0039] The alkenyl group may be partially or fully halogenated by
one or more halogen atoms, in particular by fluorine or chlorine.
The alkenyl group preferably has from 1 to 3 halogen atoms.
[0040] The alkynyl group includes straight-chain and branched
alkynyl groups. These are preferably straight-chain and branched
C.sub.3-C.sub.12-alkynyl groups and in particular
C.sub.3-C.sub.6-alkynyl groups. Examples of alkynyl groups are
2-propynyl, 2-butynyl, 3-butynyl, 1-methyl-2-propynyl, 2-pentynyl,
3-pentynyl, 4-pentynyl, 1-methyl-3-butynyl, 2-methyl-3-butynyl,
1-methyl-2-butynyl, 1,1-dimethyl-2-propynyl, 1-ethyl-2-propynyl,
2-hexynyl, 3-hexynyl, 4-alkynyl [sic], 5-hexynyl,
1-methyl-2-pentynyl, 1-methyl-3-pentynyl, 1-methyl-4-pentynyl,
2-methyl-3-pentynyl, 2-methyl-4-pentynyl. 3-methyl-4-pentynyl,
4-methyl-2-pentynyl, 1,2-dimethyl-2-butynyl,
1,1-dimethyl-3-butynyl, 1,2-dimethyl-3-butynyl,
2,2-dimethyl-3-butynyl, 1-ethyl-2-butynyl, 1-ethyl-3-butynyl,
2-ethyl-3-butynyl and 1-ethyl-1-methyl-2-propynyl.
[0041] The above statements for the alkenyl group and its halogen
substituents and for the alkynyl group apply in a corresponding
manner to alkenyloxy and alkynyloxy.
[0042] The cycloalkyl group is preferably a
C.sub.3-C.sub.6cycloalkyl group, such as cyclopropyl, cyclobutyl,
cyclopentyl or cyclohexyl. If the cycloalkyl group is substituted,
it preferably has from 1 to 3 C.sub.1-C.sub.4-alkyl radicals as
substituents.
[0043] Cycloalkenyl is preferably a C.sub.4-C.sub.6-cycloalkenyl
group, such as cyclobutenyl, cyclopentenyl or cyclohexenyl. If the
cycloalkenyl group is substituted, it preferably has from 1 to 3
C.sub.1-C.sub.4-alkyl radicals as substituents.
[0044] A cycloalkoxy group is preferably a
C.sub.5-C.sub.6-cycloalkoxy group, such as cyclopentyloxy or
cyclohexyloxy. If the cycloalkoxy group is substituted, it
preferably has from 1 to 3 C.sub.1-C.sub.4-alkyl radicals as
substituents.
[0045] The cycloalkenyloxy group is preferably a
C.sub.5-C.sub.6-cycloalke- nyloxy group, such as cyclopentyloxy or
cyclohexyloxy. If the cycloalkenyloxy group is substituted, it
preferably has from 1 to 3 C.sub.1-C.sub.4-alkyl radicals as
substituents.
[0046] Aryl is preferably phenyl.
[0047] If A is a phenyl group, this may have one, two or three of
the abovementioned substituents in any position. These substituents
are preferably selected, independently of one another, from alkyl,
difluoromethyl, trifluoromethyl and halogen, in particular
chlorine, bromine and iodine. Particularly preferably, the phenyl
group has a substituent in the 2-position.
[0048] If A is a 5-membered heterocycle, it is in particular a
furyl, thiazolyl, pyrazolyl, imidazolyl, oxazolyl, thienyl,
triazolyl or thiadiazolyl radical or the corresponding dihydro or
tetrahydro derivatives thereof. Preference is given to a thiazolyl
or pyrazolyl radical.
[0049] If A is a 6-membered heterocycle, it is in particular a
pyridyl radical or a radical of the formula: 7
[0050] in which one of the radicals X and Y is O, S or NR.sup.23,
where R.sup.23 is H or alkyl, and the other of the radicals X and Y
is CH.sub.2, S, SO, SO.sub.2 or NR.sup.23. The dotted line means
that a double bond may or may not be present.
[0051] The 6-membered aromatic heterocycle is particularly
preferably a pyridyl radical, in particular a 3-pyridyl radical, or
a radical of the formula 8
[0052] in which X is CH.sub.2, S, SO or SO.sub.2.
[0053] The abovementioned heterocyclic radicals may or may not have
1, 2 or 3 of the abovementioned substituents, where these
substituents are preferably selected, independently of one another,
from alkyl, halogen, difluoromethyl or trifluoromethyl.
[0054] A is particularly preferably a radical of the formulae:
9
[0055] in which R.sup.3, R.sup.4, R.sup.6, R.sup.7, R.sup.8 and
R.sup.9 independently of one another are hydrogen, alkyl, in
particular methyl, halogen, in particular chlorine, CHF.sub.2 or
CF.sub.3.
[0056] The radical R.sup.1 in the formula I is preferably a
hydrogen atom.
[0057] The radical R.sup.2 in the formula I is preferably a phenyl
radical. R.sup.2 preferably has at least one substituent which is
particularly preferably in the 2-position. The substituent (or the
substituents) is (are) preferably selected from the group
consisting of alkyl, cycloalkyl, cycloalkenyl, halogen or
phenyl.
[0058] The substituents of the radical R.sup.2 may in turn be
substituted again. The aliphatic or cycloaliphatic substituents may
be partially or fully halogenated, in particular fluorinated or
chlorinated. They preferably have 1, 2 or 3 fluorine or chlorine
atoms. If the substituent of the radical R.sup.2 is a phenyl group,
this phenyl group may preferably be substituted by from 1 to 3
halogen atoms, in particular chlorine atoms, and/or by a radical
which is preferably selected from alkyl and alkoxy. Particularly
preferably, the phenyl group is substituted with a halogen atom in
the p-position, i.e. the particularly preferred substituent of the
radical R.sup.2 is a p-halogen-substituted phenyl radical. The
radical R.sup.2 may also be condensed with a saturated 5-membered
ring, where this ring for its part may have from 1 to 3 alkyl
substituents.
[0059] R.sup.2 is in this case, for example, indanyl, thiaindanyl
and oxaindanyl. Preference is given to indanyl and 2-oxaindanyl
which are attached to the nitrogen atom in particular via the
4-position.
[0060] According to a preferred embodiment, the composition
according to the invention comprises as amide compound a compound
of the formula I in which A is as defined below:
[0061] phenyl, pyridyl, dihydropyranyl, dihydrooxathiynyl,
dihydrooxathiynyloxide, dihydrooxathiynyldioxide, furyl, thiazolyl,
pyrazolyl or oxazolyl, where these groups may have 1, 2 or 3
substituents which are selected, independently of one another, from
alkyl, halogen, difluoromethyl and trifluoromethyl.
[0062] According to a further preferred embodiment, A is one of the
following groups:
[0063] pyridin-3-yl, which may or may not be substituted in the
2-position by halogen, methyl, difluoromethyl, trifluoromethyl,
methoxy, methylthio, methylsulfynyl or methylsulfonyl;
[0064] phenyl, which may or may not be substituted in the
2-position by methyl, trifluoromethyl, chlorine, bromine or
iodine;
[0065] 2-methyl-5,6-dihydropyran-3-yl;
[0066] 2-methyl-5,6-dihydro-1,4-oxathiyn-3-yl or the 4-oxide or
4,4-dioxide thereof;
[0067] 2-methylfuran-3-yl, which may or may not be substituted in
the 4- and/or 5-position by methyl;
[0068] thiazol-5-yl, which may or may not be substituted in the 2-
and/or 4-position by methyl, chlorine, difluoromethyl or
trifluoromethyl;
[0069] thiazol-4-yl, which may or may not be substituted in the 2-
and/or 5-position by methyl, chlorine, difluoromethyl or
trifluoromethyl;
[0070] 1-methylpyrazol-4-yl, which may or may not be substituted in
the 3- and/or 5-position by methyl, chlorine, difluoromethyl or
trifluoromethyl; or
[0071] oxazol-5-yl, which may or may not be substituted in the 2-
and/or 4-position by methyl or chlorine.
[0072] According to a further preferred embodiment, the
compositions according to the invention comprise as amide compound
a compound of the formula I in which R.sup.2 is a phenyl group
which may or may not be substituted by 1, 2 or 3 of the
above-mentioned substituents.
[0073] According to a further preferred embodiment, the
compositions according to the invention comprise as amide compound
a compound of the formula I in which R.sup.2 is a phenyl group
which has one of the following substituents in the 2-position:
[0074] C.sub.3-C.sub.6-alkyl, C.sub.5-C.sub.6-cycloalkenyl,
C.sub.5-C.sub.6-cycloalkyloxy, cycloalkenyloxy, where these groups
may be substituted by 1, 2 or 3 C.sub.1-C.sub.4-alkyl groups,
[0075] phenyl, which is substituted by from 1 to 5 halogen atoms
and/or from 1 to 3 groups which are selected, independently of one
another, from C.sub.1-C.sub.4-alkyl, C.sub.1-C.sub.4-haloalkyl,
C.sub.1-C.sub.4-alkoxy, C.sub.1-C.sub.4-haloalkoxy,
C.sub.1-C.sub.4-alkylthio and C.sub.1-C.sub.4-haloalkylthio,
[0076] indanyl or oxaindanyl which may or may not be substituted by
1, 2 or 3 C.sub.1-C.sub.4-alkyl groups.
[0077] According to a further preferred embodiment, the
compositions according to the invention comprise as amide compound
a compound of the formula Ia, 10
[0078] in which
[0079] A is 11
[0080] X is methylene, sulfur, sulfynyl or sulfonyl (SO.sub.2),
[0081] R.sup.3 is methyl, difluoromethyl, trifluoromethyl,
chlorine, bromine or iodine,
[0082] R.sup.4 is trifluoromethyl or chlorine,
[0083] R.sup.5 is hydrogen or methyl,
[0084] R.sup.6 is methyl, difluoromethyl, trifluoromethyl or
chlorine,
[0085] R.sup.7 is hydrogen, methyl or chlorine,
[0086] R.sup.8 is methyl, difluoromethyl or trifluoromethyl,
[0087] R.sup.9 is hydrogen, methyl, difluoromethyl, trifluoromethyl
or chlorine,
[0088] R.sup.10 is C.sub.1-C.sub.4-alkyl, C.sub.1-C.sub.4-alkoxy,
C.sub.1-C.sub.4-alkylthio or halogen.
[0089] According to a particularly preferred embodiment, the
compositions comprise as amide compound a compound of the formula
Ib 12
[0090] in which
[0091] R.sup.4 is halogen and
[0092] R.sup.11 is phenyl which is substituted by halogen.
[0093] Useful amide compounds of the formula I are mentioned in
EP-A-545 099 and 589 301 which are incorporated herein in their
entirety by reference.
[0094] The preparation of the amide compounds of the formula I is
known, for example, from EP-A-545 099 or 589 301 or can be carried
out by similar processes.
[0095] Preferred substituents R.sup.21 and R.sup.22 are hydrogen,
F, Cl, methyl, ethyl, methoxy, thiomethyl and N-methylamino.
R.sup.3 and R.sup.4 together may also form a grouping .dbd.O.
[0096] Preferred fungicides of the dicarboximide type are the
compounds IIa to IId:
[0097] II.a: ethyl
(")-3-(3,5-dichlorophenyl)-5-methyl-2,4-dioxooxazolidin-
e-5-carboxylate [sic] 13
[0098] II.b:
3-(3,5-dichlorophenyl)-N-isopropyl-2,4-dioxoimidazolidine-1-c-
arboxamide 14
[0099] II.c:
N-(3,5-dichlorophenyl)-1,2-dimethylcyclopropane-1,2-dicarboxi- mide
15
[0100] II.d:
(RS)-3-(3,5-dichlorophenyl)-5-ethenyl-5-methyl-1,3-oxazolidin-
e-2,4-dione 16
[0101] These compounds are commercially available as fungicidally
active ingredients and are described in the literature as
follows:
[0102] II.a (common name: chlozolinate): CAS RN [84332-86-5], DE-A
29 06 574;
[0103] II.b (common name: iprodione): CAS RN [36734-19-7], U.S.
Pat. No. 3, 755,350;
[0104] II.c (common name: procymidone): CAS RN [32809-16-8], U.S.
Pat. No. 3,903,090;
[0105] II.d (common name: vinclozoline): CAS RN [50471-44-8), DE-A
22 07 576].
[0106] To unfold the synergistic activity, even a small amount of
the amide compound of the formula I is sufficient. Preference is
given to employing amide compound and active ingredient of the
formula II and/or III to IX in a weight ratio in the range of from
50:1 to 1:50, in particular from 10:1 to 1:10. It is also possible
here to employ ternary mixtures which, in addition to amide
compounds I, comprise both compounds II and one or more compounds
III to IX. In such mixtures, the mixing ratio of the compounds II
and III to IX with each other is usually in the range of from 50:1
to 1:50, preferably from 10:1 to 1:10.
[0107] Owing to the basic character of their nitrogen atoms, the
compounds III, IV, V and VIII are capable of forming salts or
adducts with inorganic or organic acids or with metal ions.
[0108] Examples of inorganic acids are hydrohalic acids such as
hydrofluoric acid, hydrochloric acid, hydrobromic acid and
hydriodic acid, sulfuric acid, phosphoric acid and nitric acid.
[0109] Suitable organic acids are, for example, formic acid,
carbonic acid [sic) and alkanoic acids, such as acetic acid,
trifluoroacetic acid, trichloroacetic acid and propionic acid, and
also glycolic acid, thiocyanic acid, lactic acid, succinic acid,
citric acid, benzoic acid, cinnamic acid, oxalic acid,
alkylsulfonic acids (sulfonic acids having straight-chain or
branched alkyl radicals of 1 to 20 carbon atoms), arylsulfonic
acids or aryldisulfonic acids (aromatic radicals, such as phenyl
and naphthyl, which carry one or two sulfo groups), alkylphosphonic
acids (phosphonic acids having straight-chain or branched alkyl
radicals of 1 to 20 carbon atoms), arylphosphonic acids or
aryldiphosphonic acids (aromatic radicals, such as phenyl and
naphthyl, which carry one or two phosphoric [sic] acid radicals),
it being possible for the alkyl or aryl radicals to carry further
substituents, eg. p-toluenesulfonic acid, salicylic acid,
p-aminosalicylic acid, 2-phenoxybenzoic acid, 2-acetoxybenzoic
acid, etc.
[0110] Suitable metal ions are, in particular, the ions of the
elements of the first to eighth sub-group, in particular chromium,
manganese, iron, cobalt, nickel, copper, zinc and furthermore of
the second main group, in particular calcium and magnesium, and of
the third and fourth main group, in particular aluminum, tin and
lead. The metals can exist in the various valencies which they can
assume.
[0111] When preparing the mixtures, it is preferred to employ the
pure active ingredients I and II to IX, to which further active
ingredients against harmful fungi or other pests, such as insects,
arachnids or nematodes, or else herbicidal or growth-regulating
active ingredients or fertilizers, can be admixed.
[0112] The mixtures of the compounds I and II and/or III to IX, or
the compounds I and II and/or III to IX used simultaneously,
jointly or separately, exhibit outstanding activity against a wide
range of phytopathogenic fungi, in particular from the classes of
the Ascomycetes, Basidiomycetes, Phycomycetes and Deuteromycetes.
Some of them act systemically and can therefore be employed as
foliar- and soil-acting fungicides.
[0113] They are especially important for controlling a large number
of fungi in a variety of crop plants, such as cotton, vegetable
species (eg. cucumbers, beans, tomatoes, potatoes and cucurbits),
barley, grass, oats, bananas, coffee, maize, fruit species, rice,
rye, soya, grapevine, wheat, ornamentals, sugar cane, and a variety
of seeds.
[0114] They are particularly suitable for controlling the following
phytopathogenic fungi: Erysiphe graminis (powdery mildew) in
cereals, Erysiphe cichoracearum and Sphaerotheca fuliginea in
cucurbits, Podosphaera leucotricha in apples, Uncinula necator in
grapevines, Puccinia species in cereals, Rhizoctonia species in
cotton, rice and lawns, Ustilago species in cereals and sugar cane,
Venturia inaequalis (scab) in apples, Helminthosporium species in
cereals, Septoria nodorum in wheat, Botrytis cinera [sic] (gray
mold) in strawberries, vegetables, ornamentals and grapevines,
Cercospora arachidicola in groundnuts, Pseudocercosporella
herpotrichoides in wheat and barley, Pyricularia oryzae in rice,
Phytophthora infestans in potatoes and tomatoes, Plasmopara
viticola in grapevines, Pseudoperonospora species in hops and
cucumbers, Alternaria species in vegetables and fruit,
Mycosphaerella species in bananas and Fusarium and Verticillium
species.
[0115] The mixtures according to the invention may particularly
preferably be employed for controlling Botrytis species in crops of
grapevines and vegetables, and also in ornamentals.
[0116] The compounds I and II and/or III to IX can be applied
simultaneously, either together or separately, or in succession,
the sequence, in the case of separate application, generally not
having any effect on the result of the control measures.
[0117] Depending on the kind of effect desired, the application
rates of the mixtures according to the invention are, in particular
in agricultural crop areas, from 0.01 to 8 kg/ha, preferably 0.1 to
5 kg/ha, in particular 0.2 to 3.0 kg/ha.
[0118] The application-rates of the compounds I are from 0.01 to
2.5 kg/ha, preferably 0.05 to 2.5 kg/ha, in particular 0.1 to 1.0
kg/ha.
[0119] Correspondingly, in the case of the compounds II and/or III
to IX, the application rates are from 0.01 to 10 kg/ha, preferably
0.05 to 5 kg/ha, in particular 0.05 to 2.0 kg/ha.
[0120] For seed treatment, the application rates of the mixture are
generally from 0.001 to 250 g/kg of seed, preferably 0.01 to 100
g/kg, in particular 0.01 to 50 g/kg.
[0121] If phytopathogenic harmful fungi are to be controlled, the
separate or joint application of the compounds I and II and/or III
to IX or of the mixtures of the compounds I and II and/or III to IX
is effected by spraying or dusting the seeds, the plants or the
soils before or after sowing of the plants, or before or after
plant emergence.
[0122] The fungicidal synergistic mixtures according to the
invention, or the compounds I and II and/or III to IX, can be
formulated for example in the form of ready-to-spray solutions,
powders and suspensions or in the form of highly concentrated
aqueous, oily or other suspensions, dispersions, emulsions, oil
dispersions, pastes, dusts, materials for broadcasting or granules,
and applied by spraying, atomizing, dusting, broadcasting or
watering. The use form depends on the intended purpose; in any
case, it should ensure as fine and uniform as possible a
distribution of the mixture according to the invention.
[0123] The formulations are prepared in a known manner, eg. by
extending the active ingredient with solvents and/or carriers, if
desired using emulsifiers and dispersants, it being possible also
to use other organic solvents as auxiliary solvents if water is
used as the diluent. Suitable auxiliaries for this purpose are
essentially: solvents such as aromatics (eg. xylene), chlorinated
aromatics (eg. chlorobenzenes), paraffins (eg. mineral oil
fractions), alcohols (eg. methanol, butanol), ketones (eg.
cyclohexanone), amines (eg. ethanolamine, dimethylformamide) and
water; carriers such as ground natural minerals (eg. kaolins,
clays, talc, chalk) and ground synthetic minerals (eg. finely
divided silica, silicates); emulsifiers such as nonionic and
anionic emulsifiers (eg. polyoxyethylene fatty alcohol ethers,
alkylsulfonates and arylsulfonates) and dispersants such as
lignosulfite waste liquors and methylcellulose.
[0124] Suitable surfactants are the alkali metal salts, alkaline
earth metal salts and ammonium salts of aromatic sulfonic acids,
eg. ligno-, phenol-, naphthalene- and dibutylnaphthalenesulfonic
acid, and of fatty acids, alkyl- and alkylarylsulfonates, alkyl,
lauryl ether and fatty alcohol sulfates, and salts of sulfated
hexa-, hepta- and octadecanols, or of fatty alcohol glycol ethers,
condensates of sulfonated naphthalene and its derivatives with
formaldehyde, condensates of naphthalene or of the
naphthalenesulfonic acids with phenol and formaldehyde,
polyoxyethylene octylphenol ether, ethoxylated isooctyl-, octyl- or
nonylphenol, alkylphenol polyglycol ethers, tributylphenyl
polyglycol ethers, alkylaryl polyether alcohols, isotridecyl
alcohol, fatty alcohol/ethylene oxide condensates, ethoxylated
castor oil, polyoxyethylene alkyl ethers or polyoxypropylene [sic],
lauryl alcohol polyglycol ether acetate, sorbitol esters,
lignosulfite waste liquors or methylcellulose.
[0125] Powders, materials for broadcasting and dusts can be
prepared by mixing or jointly grinding the compounds I or II and/or
III to IX, or the mixture of the compounds I and II and/or III to
IX, with a solid carrier.
[0126] Granules (eg. coated granules, impregnated granules or
homogeneous granules) are usually prepared by binding the active
ingredient, or active ingredients, to a solid carrier.
[0127] Fillers or solid carriers are, for example, mineral earths,
such as silica gel, silicas, silica gels [sic], silicates, talc
kaolin, limestone, lime, chalk, bole, loess, clay, dolomite,
diatomaceous earth, calcium sulfate, magnesium sulfate, magnesium
oxide, ground synthetic materials and fertilizers, such as ammonium
sulfate, ammonium phosphate, ammonium nitrate, ureas, and products
of vegetable origin, such as cereal meal, tree bark meal, wood meal
and nutshell meal, cellulose powders or other solid carriers.
[0128] The formulations generally comprise from 0.1 to 95% by
weight, preferably 0.5 to 90% by weight, of one of the compounds I
and II and/or III to IX or of the mixture of the compounds I and II
and/or III to IX. The active ingredients are employed in a purity
of from 90% to 100%, preferably 95% to 100% (according to NMR or
HPLC spectrum [sic]).
[0129] The compounds I and II and/or III to IX, the mixtures, or
the corresponding formulations, are applied by treating the harmful
fungi, their habitat, or the plants, seeds, soils, areas,
[0130] VII. An intimate mixture of 30 parts by weight of the active
ingredients, 92 parts by weight of pulverulent silica gel and 8
parts by weight of paraffin oil which had been sprayed onto the
surface of this silica gel; this formulation imparts good adhesion
to the active ingredient;
[0131] VIII. A stable aqueous dispersion of 40 parts by weight of
the active ingredients, 10 parts by weight of the sodium salt of a
phenolsulfonic acid/urea/formaldehyde condensate, 2 parts by weight
of silica gel and 48 parts by weight of water; this dispersion may
be diluted further;
[0132] IX. A stable oily dispersion of 20 parts by weight of the
active ingredients, 2 parts by weight of the calcium salt of
dodecylbenzenesulfonate, 8 parts by weight of fatty alcohol
polyglycol ether, 20 parts by weight of the sodium salt of a
phenolsulfonic acid/urea/formaldehyde condensate and 88 parts by
weight of a paraffinic mineral oil.
USE EXAMPLE
[0133] The synergistic activity of the mixtures according to the
invention can be demonstrated by the following experiments:
[0134] The active ingredients, separately or together, are
formulated as a 10% emulsion in a mixture of 63% by weight of
cyclohexanone and 27% by weight of emulsifier, and diluted with
water to the desired concentration.
[0135] Evaluation is carried out by determining the infected leaf
areas in percent. These percentages are converted into efficacies.
The efficacy (w) is calculated as follows using Abbot's
formula:
W=(1-.alpha.).multidot.100/.beta.
[0136] .alpha. corresponds to the fungal infection of the treated
plants in % and
[0137] .beta. corresponds to the fungal infection of the untreated
(control) plants in %
[0138] An efficacy of 0 means that the infection level of the
treated plants corresponds to that of the untreated control plants;
an efficacy of 100 means that the treated plants were not
infected.
[0139] The expected efficacies of the mixtures of the active
ingredients were determined using Colby's formula (R. S. Colby,
Weeds 15, 20-22 (1967)] and compared with the observed
efficacies.
Colby formula: E=x+y-x.multidot.y/100
[0140] E expected efficacy, expressed in % of the untreated
control, when using the mixture of the active ingredients A and B
at the concentrations a and b
[0141] x efficacy, expressed in % of the untreated control, when
using active ingredient A at a concentration of a
[0142] y efficacy, expressed in % of the untreated control, when
using active ingredient B at a concentration of b
Use Example 1
Activity Against Botrytis cinerea on Bell Pepper Leaves
[0143] Bell pepper seedlings of the variety "Neusiedler Ideal
Elite" were, after 4-5 leaves were well developed, sprayed to
runoff point with an aqueous preparation of active ingredient which
had been prepared from a stock solution comprising 10% of active
ingredient, 63% of cyclohexanone and 27% of emulsifier. The next
day, the treated plants were inoculated with a spore suspension of
Botrytis cinerea containing 1.7.times.10.sup.6 spores per ml of a
2% strength aqueous Biomalz solution. The test plants were
subsequently placed in a climatized chamber with high atmospheric
humidity at 22-24.degree. C. After 5 days, the extent of the fungal
infection on the leaves could be determined visually in %.
[0144] The compounds of the formula I used were the following
components: 17
[0145] The results are shown in Tables 1 and 2 below.
1TABLE 1 Concentration of active ingredient in Active the spray
liquor Efficacy in % of the Ex. ingredient in ppm untreated control
1C untreated 0 0 (99% infection) 2C Compound I.1 31 78 16 67 8 11
3C Compound I.2 31 67 16 44 8 44 4C Compound VIa 31 0 16 0 8 0 5C
Compound VII 31 0 16 0 8 0 6C Compound IXa 31 0 16 0 8 0
[0146]
2 TABLE 2 Mixtures according to the invention observed calculated
Ex. (content in ppm) efficacy efficacy*) 7 31 ppm I.1 97 78 + 31
ppm VIa 8 8 ppm I.1 30 11 + 8 ppm VIa 9 31 ppm I.2 100 67 + 31 ppm
VIa 10 16 ppm I.2 70 44 + 16 ppm VIa 11 31 ppm I.1 90 78 + 31 ppm
VII 12 8 ppm I.1 39 11 + 8 ppm VII
[0147]
3TABLE 3 Concentration of active ingredient Efficacy in % of Active
in the spray the untreated Ex. ingredient liquor in ppm control 21C
untreated 0 0 (100% infection) 22C Compound I.1 31 0 16 0 23C
Compound I.2 31 20 16 0 24C Compound IV 31 0 16 0 25C Compound VIa
31 0 26C Compound VII 31 0 27C Compound VIII 31 0 16 0
[0148]
4 TABLE 4 Mixtures according to the invention observed calculated
Ex. (content in ppm) efficacy efficacy*) 28 31 ppm I.1 50 0 + 0 31
ppm IV 0 29 16 ppm I.1 20 0 + 0 16 ppm IV 0 30 31 ppm I.2 70 20 + 0
31 ppm IV 0 31 16 ppm I.2 20 0 + 0 16 ppm IV 0 32 31 ppm I.2 50 20
+ 0 31 ppm IVa 0 33 31 ppm I.2 40 20 + 0 31 ppm VII 0 34 31 ppm I.1
30 0 + 0 31 ppm VIII 0 35 16 ppm I.2 20 0 + 0 16 ppm VIII 0
*)calculated using Colby's formula
[0149] The test results show that for all mixing ratios the
observed efficacy is higher than the efficacy which had been
calculated beforehand using Colby's formula.
* * * * *